The present invention relates to novel a-amino acid derivatives of formula I below. It relates to the preparation of those substances and to agrochemical compositions comprising at least one of those compounds as active ingredient. The invention relates also to the preparation of the said compositions and to the use of the compounds or of the compositions in controlling or preventing the infestation of plants by phytopathogenic microorganisms, especially fungi.
The invention relates to compounds of the general formula I 
as well as possible isomers and mixtures of isomers thereof,
wherein
n is a number zero or one; and
R1 is C1-C12alkyl that is unsubstituted or may be substituted by C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfonyl, C3-C8cycloalkyl, cyano, C1-C6alkoxycarbonyl, C3-C6alkenyloxycarbonyl or by C3-C6alkynyloxycarbonyl; C3-C8cycloalkyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12haloalkyl; or a group NR11R12 wherein R11 and R12 are each independently of the other hydrogen or C1-C6alkyl, or together are tetra- or penta-methylene;
R2 and R3 are each independently of the other hydrogen; C1-C8alkyl; C1-C8alkyl substituted by hydroxy, C1-C4alkoxy, mercapto or by C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl; C3-C8cycloalkyl; C1-C4alkyl; or the two groups R2 and R3 together with the carbon atom to which they are bonded form a three- to eight-membered ring;
R4, R5, R6 and R7 are identical or different and are each independently of the others hydrogen or C1-C4alkyl;
R8 is C1-C6alkyl, C3-C6alkenyl or C3-C6alkynyl;
A is C1-C6alkylene; and
B is optionally mono- or poly-nuclear, unsubstituted or substituted aryl; optionally mono- or poly-nuclear, unsubstituted or substituted heteroaryl; C4-C12alkyl; or C3-C8cycloalkyl.
Examples of aryl in the above-mentioned sense are:
phenyl, naphthyl, anthracenyl, phenanthrenyl.
Examples of heteroaryl are:
furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl, naphthyridinyl.
Examples of substituents of those aryl or heteroaryl groups are:
alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, phenyl, phenyl-alkyl, it being possible for those groups to carry one or more identical or different halogen atoms; alkoxy; alkenyloxy; alkynyloxy; alkoxyalkyl; haloalkoxy, alkylthio; haloalkylthio; alkylsulfonyl; formyl; alkanoyl; hydroxy; halogen; cyano; nitro; amino; alkylamino; dialkylamino; carboxy; alkoxycarbonyl; alkenyloxycarbonyl; alkynyloxycarbonyl.
In the above formula I, xe2x80x9chalogenxe2x80x9d includes fluorine, chlorine, bromine and iodine.
The alkyl, alkenyl and alkynyl radicals may be straight-chain or branched, and this applies also to the alkyl, alkenyl or alkynyl moiety of other alkyl-, alkenyl- or alkynyl-containing groups.
Depending upon the number of carbon atoms mentioned, alkyl on its own or as part of another substituent is to be understood as being, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the isomers thereof, for example isopropyl, isobutyl, tert-butyl or sec-butyl, isopentyl or tert-pentyl. Cycloalkyl is, depending upon the number of carbon atoms mentioned, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
Depending upon the number of carbon atoms mentioned, alkenyl as a group or as a structural element of other groups is to be understood as being, for example, ethenyl, allyl, buten-2-yl, buten-3-yl, penten-1-yl, penten-3-yl, hexen-1-yl, 4-methyl-3-pentenyl or 4-methyl-3-hexenyl.
Alkynyl as a group or as a structural element of other groups is, for example, ethynyl, propyn-1-yl, propyn-2-yl, butyn-1-yl, butyn-2-yl, 1-methyl-2-butynyl, hexyn-1-yl, 1-ethyl-2-butynyl, octyn-1-yl.
A haloalkyl group may have one or more (identical or different) halogen atoms, for example CHCl2, CH2F, CCl3, CH2Cl, CHF2, CF3, CH2CH2Br, C2Cl5, CH2Br, CHClBr, CF3CH2, etc.
The presence of at least one asymmetric carbon atom and/or at least one asymmetric sulfur atom in the compounds of formula I means that the compounds may occur in optically isomeric forms. As a result of the presence of a possible aliphatic Cxe2x95x90C double bond, geometric isomerism may also occur. Formula I is intended to include all those possible isomeric forms and mixtures thereof.
Preference is given to compounds of formula I wherein
R1 is C1-C12alkyl; C3-C8cycloalkyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12haloalkyl; or a group NR11R12 wherein R11 and R12 are each independently of the other hydrogen or C1-C6alkyl, or together are tetra- or penta-methylene;
R2 is hydrogen;
R3 is C1-C8alkyl; C1-C8alkyl substituted by hydroxy, C1-C4alkoxy, mercapto or by C1-C4alkyl-thio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl; or C3-C8cycloalkyl-C1-C4alkyl;
B is phenyl; naphthyl; or heteroaryl that is formed from one or two five- or six-membered rings and that may contain from 1 to 4 identical or different hetero atoms selected from nitrogen, oxygen and sulfur; wherein the phenyl, naphthyl or heteroaryl may optionally carry from 1 to 5 identical or different substituents selected from:
C1-C8alkyl, C2-C28alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, phenyl, phenyl-C1-C4alkyl, those groups being unsubstituted or mono- to per-halogenated and the halogen atoms being identical or different; C1-C8alkoxy; C3-C8alkenyloxy; C3-C8alkynyloxy; C1-C4alkoxy-C1-C4alkyl; C1-C8haloalkoxy; C1-C8alkylthio; C1-C8haloalkylthio; C1-C8alkyl-sulfonyl; formyl; C2-C8alkanoyl; hydroxy; halogen; cyano; nitro; amino; C1-C8alkylamino; C1-C8dialkylamino; carboxy; C1-C8alkoxycarbonyl; C3-C8alkenyloxycarbonyl; and C3-C8alkynyloxycarbonyl (sub-group A).
Within the scope of sub-group A, special mention should be made of those compounds of formula I wherein
R1 is C1-C6alkyl; C5-C6cycloalkyl; C2-C6alkenyl; C1-C6haloalkyl; or a group NR11R12 wherein
R11 and R12 are each independently of the other hydrogen or C1-C6alkyl;
R3 is C1-C8alkyl; or C3-C6cycloalkyl;
R4 is hydrogen or C1-C4alkyl;
R5, R6 and R7 are hydrogen;
R8 is C1-C6alkyl;
A is C1-C2alkylene; and
B is phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyi, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, benzothiazolyl or benzoxazolyl, each unsubstituted or substituted by from 1 to 5 substituents selected from: C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8-cycloalkyl-C1-C4alkyl, phenyl, phenyl-C1-C4alkyl, those groups being unsubstituted or mono- to per-halogenated and the halogen atoms being identical or different; C1-C8alkoxy; C3-C8-alkenyloxy; C3-C8alkynyloxy; C1-C4alkoxy-C1-C4alkyl; C1-C8haloalkoxy; C1-C8alkylthio; C1-C8-haloalkylthio; C1-C8alkylsulfonyl; formyl; C2-C8alkanoyl; hydroxy; halogen; cyano; nitro; amino; C1-C8alkylamino; C1-C8dialkylamino; carboxy; C1-C8alkoxycarbonyl; C3-C8alkenyl-oxycarbonyl; and C3-C8alkynyloxycarbonyl (sub-group B).
Within the scope of sub-group B, special preference is given to a group of compounds of formula I wherein
n is the number one;
R1 is C1-C6alkyl; C1-C6haloalkyl; or a group NR11R12 wherein R11 and R12 are each independently of the other C1-C4alkyl;
R3 is C3-C4alkyl; or cyclopropyl;
R4 is hydrogen or methyl;
R8 is C1-C2alkyl;
A is methylene; and
B is phenyl, naphthyl, furyl, thienyl, pyridyl, pyrimidinyl, triazinyl, benzothiophenyl, each unsubstituted or substituted by from 1 to 3 substituents selected from: C1-C8alkyl, phenyl, those groups being unsubstituted or mono- to per-halogenated and the halogen atoms being identical or different; C1-C8alkoxy; C3-C8alkenyloxy; C3-C8alkynyloxy; C1-C8haloalkoxy; C1-C8alkylthio; C1-C8haloalkylthio; C1-C8alkylsulfonyl; formyl; C1-C8alkanoyl; hydroxy; halogen; cyano; nitro; and C1-C8alkoxycarbonyl (sub-group Ca).
A special group within the scope of sub-group Ca comprises compounds of formula I wherein
R1 is C1-C4alkyl; or dimethylamino;
R3 is 2-propyl;
R8 is methyl;
B is phenyl, naphthyl, each unsubstituted or substituted by from 1 to 3 substituents selected from: C1-C8alkyl, C1-C8haloalkyl, C1-C8alkoxy, C1-C8haloalkoxy, C1-C8alkylthio, C1-C8haloalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl (sub-group Cb).
Another especially preferred group within the scope of sub-group Ca comprises compounds of formula I wherein
R1 is C1-C4alkyl; or dimethylamino;
R3 is 2-propyl;
R8 is methyl;
B is thienyl, pyridyl, each unsubstituted or substituted by from 1 to 3 substituents selected from: C1-C8alkyl, C1-C8haloalkyl, C1-C8alkoxy, C1-C8haloalkoxy, C1-C8alkylthio, C1-C8haloalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl (sub-group Cc).
Certain xcex1-amino acid derivatives having a different kind of structure have already been proposed for controlling plant-destructive fungi (for example in EP-398 072, EP-425 925, DE-4 026 966, EP-477 639, EP493 683, DE-4 035 851, EP-487 154, EP-496 239, EP-550 788 and EP-554 729). The action of those preparations is not, however, satisfactory. Surprisingly, with the compound structure of formula I, new kinds of microbicides having a high level of activity have been found.
The compounds of formula I can be prepared as follows:
a) by reacting a substituted amino acid of formula II 
xe2x80x83wherein the radicals R1 R2 and R3 and n are as defined above, or a carboxy-activated derivative thereof, if desired in the presence of a catalyst, if desired in the presence of an acid-binding agent and if desired in the presence of a diluent,
with an amine of formula III 
xe2x80x83wherein R4, R5, R6, R7, R8, A and B are as defined above.
The amino acid derivatives of formula II required for carrying out Process a) according to the invention are known per se.
The amines of formula III are novel and the invention relates also thereto.
The amines of formula III can be prepared in accordance with Process aa) described below.
Suitable carboxy-activated derivatives of the amino acid of formula II include any carboxy-activated derivatives, such as acid halides, for example acid chlorides; also symmetrical or mixed anhydrides, for example the mixed O-alkylcarboxylic acid anhydrides; and also activated esters, for example p-nitrophenyl esters or N-hydroxysuccinimide esters, and activated forms of the amino acid produced in situ using condensing agents, e.g. dicyclohexylcarbodiimide, carbonyldiimidazole, O-(benzotriazol-1-yl)-N,N,Nxe2x80x2,Nxe2x80x2-bis(pentamethylene)uronium hexafluorophosphate, O-(benzotriazol-1-yl)-N ,N ,Nxe2x80x2,Nxe2x80x2-bis(tetramethylene)uronium hexafluorophosphate, (benzotriazol-1-yloxy)-tripyrrolidinophosphonium hexafluorophosphate, (benzotriazol-1-yloxy)-tris(dimethylamino)phosphonium hexafluorophosphate or O-(benzotriazol-1-yl)-N,N,Nxe2x80x2,Nxe2x80x2-tetramethyluronium hexafluorophosphate.
The mixed anhydrides corresponding to the amino acid of formula II can be prepared by reacting the amino acid of formula II with a chloroformic acid ester, for example a chloroformic acid alkyl ester, preferably isobutyl chloroformate, if desired in the presence of an acid-binding agent, such as an inorganic or organic base, for example a tertiary amine, e.g. triethylamine, pyridine, N-methylpiperidine or N-methylmorpholine.
The reaction of the amino acid of formula II, or of a carboxy-activated derivative of the amino acid of formula II, with an amine of formula III is carried out in an inert diluent, such as an aromatic, non-aromatic or halogenated hydrocarbon, for example a chlorinated hydrocarbon, e.g. methylene chloride or toluene; a ketone, e.g. acetone; an ester, e.g. ethyl acetate; an amide, e.g. dimethylformamide; a nitrile, e.g. acetonitrile; or an ether, e.g. tetrahydrofuran, dioxane, diethyl ether or tert-butyl methyl ether; or in a mixture of those inert diluents, if desired in the presence of an acid-binding agent, such as an inorganic or organic base, for example a tertiary amine, e.g. triethylamine, pyridine, N-methylpiperidine or N-methylmorpholine, at temperatures of from xe2x88x9280 to +150xc2x0 C., preferably from xe2x88x9240 to +40xc2x0 C.
b) by oxidising a compound of formula Ixe2x80x2
xe2x80x83wherein R1, R2, R3, R4, R5, R6, R7, R8, A and B are as defined above, with the proviso that none of the substituents R1, R2, R3 and B contains a thiol or alkylthio group.
Suitable oxidising agents include both organic oxidising agents, such as alkyl hydroperoxides, for example cumyl hydroperoxide, and inorganic oxidising agents, such as peroxides, for example hydrogen peroxide, and transition metal oxides, for example chromium trioxide, and transition metal oxide salts, for example potassium permanganate, potassium dichromate or sodium dichromate.
The reaction of a compound of formula Ixe2x80x2 with an oxidising agent is carried out in an inert diluent, such as water or a ketone, for example acetone, or in a mixture of those inert diluents, if desired in the presence of an acid or it desired in the presence of a base, at temperatures of from xe2x88x9280 to +150xc2x0 C.
c) by reacting a compound of formula IV 
xe2x80x83wherein R1, R2, R3, R4, R5, R6, R7, R8 and n are as defined above, with a compound of formula V
Yxe2x80x94Axe2x80x94xe2x89xa1xe2x80x94Bxe2x80x83xe2x80x83V
wherein A and B are as defined above and wherein Y is a leaving group.
Suitable leaving groups include halides, for example chlorides or bromides, and sulfonates, for example tosylates, mesylates or triflates.
The reaction of a compound of formula IV with a compound of formula V is carried out in an inert diluent. The following may be mentioned as examples: aromatic, non-aromatic or halogenated hydrocarbons, e.g. toluene or methylene chloride; ketones, e.g. acetone; esters, e.g. ethyl acetate; amides, e.g. dimethylformamide; nitrites, e.g. acetonitrile; ethers, e.g. tetrahydrofuran, dioxane, diethyl ether or tert-butyl methyl ether; alcohols, e.g. methanol, ethanol, n-butanol, isopropanol or tert-butanol; dimethyl sulfoxide; or water; or mixtures of those inert diluents. The reaction of a compound of formula IV with a compound of formula V is carried out if desired in the presence of an acid-binding agent. Suitable acid-binding agents include inorganic or organic bases, for example alkali metal or alkaline earth metal hydroxides, alcoholates or carbonates, e.g. sodium hydroxide, potassium hydroxide, sodium methanolate, potassium methanolate, sodium ethanolate, potassium ethanolate, sodium tert-butanolate, potassium tert-butanolate, sodium carbonate or potassium carbonate. The temperatures are from xe2x88x9280 to +200xc2x0 C., preferably from 0 to +120xc2x0 C.
d) by reacting a sulfonic acid or sulfinic acid, or a sulfonic acid or sulfinic acid derivative, of formula VI 
xe2x80x83wherein R1 and n are as defined above and wherein X is an OH group or a leaving group, respectively, with an amine of formula VII 
xe2x80x83wherein R2, R3, R4, R5, R6, R7, R8, A and B are as defined above.
The invention relates also to compounds of formula VII and to their preparation.
The sulfonic acid or sulfinic acid, or sulfonic acid or sulfinic acid derivatives, of formula VI required for Process d) are known parse. The amines of formula VII also required are novel and the invention relates also thereto; they can be prepared in accordance with Process bb) below.
Suitable sulfonic acid or sulfinic acid derivatives of formula VI include any compounds wherein X is a leaving group, such as sulfonic acid halides or sulfinic acid halides, e.g. sulfochlorides or sulfinic acid chlorides; also symmetrical or mixed anhydrides; and also activated forms of sulfonic acid or sulfinic acid produced in situ using condensing agents, such as dicyclohexylcarbodiimide or carbonyldiimidazole.
The reaction of the sulfonic acid or sulfinic acid, or of the sulfonic acid or sulfinic acid derivative, of formula VI with an amine of formula VII is carried out in an inert diluent, such as an aromatic, non-aromatic or halogenated hydrocarbon, for example a chlorinated hydrocarbon, e.g. methylene chloride or toluene; a ketone, e.g. acetone; an ester, e.g. ethyl acetate; an amide, e.g. dimethylformamide; a nitrile, e.g. acetonitrile; or an ether, e.g. tetrahydrofuran, dioxane, diethyl ether or tert-butyl methyl ether; or water; or in a mixture of those inert diluents, if desired in the presence of an acid-binding agent, such as an inorganic or organic base: for example an alkali metal or alkaline earth metal hydroxide or carbonate, e.g. sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, or, for example, a tertiary amine, e.g. triethylamine, pyridine, N-methylpiperidine or N-methylmorpholine, at temperatures of from xe2x88x9280 to +150xc2x0 C., preferably from xe2x88x9220 to +60xc2x0 C.
e) by reacting an alkyne of formula Ixe2x80x3
xe2x80x83wherein R1, R2, R3, R4, R5, R6, R7, R8, A and n are as defined above, with an aryl or heteroaryl halide, preferably an aryl or heteroaryl iodide.
Alkynes of formula Ixe2x80x3 are known, for example, from WO 95/30651.
The reaction of the alkyne of formula Ixe2x80x3 with an aryl or heteroaryl halide is carried out in an inert diluent, such as an aromatic, non-aromatic or halogenated hydrocarbon, for example a chlorinated hydrocarbon, e.g. methylene chloride, chloroform or toluene; an amide, e.g. dimethylformamide; an ether, e.g. dioxane or tetrahydrofuran; or a sulfoxide, e.g. dimethyl sulfoxide; or in a mixture of those inert diluents, if desired in the presence of an acid-binding agent, such as an inorganic or organic base, for example a tertiary amine, e.g. triethylamine, N-methylpiperidine or pyridine, if desired in the presence of one or more transition metal salts, for example a copper halide or palladium halide, e.g. copper iodide or palladium dichloride, and if desired in the presence of one or more transition metal complexes or transition metal complex salts, such as a bis(triaryl- or trialkyl-)palladium dihalide, e.g. bis(triphenylphosphine)palladium dichloride, at temperatures of from xe2x88x9280 to +200xc2x0 C., preferably from 0 to +60xc2x0 C.
Important intermediates can be prepared as follows:
aa) The amines of formula III can be prepared in accordance with the following process variants: 
Step A comprises the alkylation of a phenol with a compound of formula V. The reaction is carried out as described under Process c).
Step B comprises the reaction of an aromatic aldehyde with nitromethane. The reaction of the two reactants is carried out in an inert diluent, such as an organic carboxylic acid, for example acetic acid, optionally in the presence of the ammonium salt of that carboxylic acid, for example ammonium acetate, at temperatures of from 0xc2x0 to +200xc2x0 C.
Step C comprises the reduction of an unsaturated nitrogen compound. The reaction is carried out in an inert diluent, such as an ether, for example diethyl ether, dioxane or tetrahydrofuran, or an alcohol, for example methanol, ethanol or isopropanol, with boron hydride, a boron hydride complex, for example the complex of boron hydride and tetrahydrofuran, an alkali metal borohydride, an alkali metal aluminum hydride, for example lithium aluminum hydride, or an aluminum alkoxyhydride, or with hydrogen if desired in the presence of a transition metal or a transition metal compound, for example nickel, at temperatures of from xe2x88x9250xc2x0 to +250xc2x0 C.
Step D comprises the reaction of an aldehyde or a ketone with hydroxylamine or a hydroxylamine salt. The reaction is carried out in an inert diluent, such as an alcohol, for example methanol, ethanol or isopropanol, an ether, for example diethyl ether, dioxane or tetrahydrofuran, an amide, for example dimethylformamide, or in water, or in a mixture of those inert diluents, if desired in the presence of an organic or inorganic base, such as a tertiary amine, for example triethylamine, a nitrogen-containing heteroaromatic compound, for example pyridine, an alkali metal or alkaline earth metal carbonate or hydrogen carbonate, for example sodium carbonate or potassium carbonate, at temperatures of from xe2x88x9220xc2x0 to +150xc2x0 C.
Step E comprises the hydrolysis of a lower alkyl ester. The reaction is carried out in an inert diluent, such as an alcohol, for example methanol, ethanol or isopropanol, an ether, for example diethyl ether, dioxane or tetrahydrofuran, a halogenated hydrocarbon, for example dichloromethane, or in water, or in a mixture of those inert diluents, if desired in the presence of a base, such as an alkali metal or alkaline earth metal hydroxide, for example lithium hydroxide, sodium hydroxide or potassium hydroxide, or in the presence of an acid, for example sulfuric acid, hydrochloric acid or trifluoroacetic acid, at temperatures of from xe2x88x9220xc2x0 to +160xc2x0 C.
Step F comprises the reaction of a carboxylic acid or an activated derivative of that carboxylic acid with hydrazoic acid or with a salt of that acid. Suitable carboxy-activated derivatives include any carboxy-activated derivatives, such as acid halides, for example acid chlorides; and also symmetrical or mixed anhydrides, for example the mixed O-alkylcarboxylic acid anhydrides. Suitable salts of hydrazoic acid include, for example, alkali metal or alkaline earth metal azides, for example sodium azide. The reaction is carried out in a diluent, such as a hydrocarbon, for example toluene or xylene, a halogenated hydrocarbon, for example chloroform, an ether, for example dioxane, a ketone, for example acetone or methyl ethyl ketone, an alcohol, for example tert-butanol, or in water, or in a mixture of those diluents, if desired in the presence of an acid, such as an inorganic acid, for example sulfuric acid or hydrochloric acid, at temperatures of from xe2x88x9240xc2x0 to +200xc2x0 C.
bb) The required amines of formula VII can be prepared in accordance with the following reaction sequence 
In a first step, an amino acid derivative of the general formula XIII, or a carboxy-activated derivative thereof, is reacted, if desired in the presence of a catalyst, if desired in the presence of an acid-binding agent and if desired in the presence of a diluent, with an amine of the general formula XII.
Suitable carboxy-activated derivatives of the amino acid of formula XIII include any carboxy-activated derivatives, such as acid halides, for example acid chlorides; also symmetrical or mixed anhydrides, for example the mixed O-alkylcarboxylic acid anhydrides; and also activated esters, for example p-nitrophenyl esters or N-hydroxysuccinimide esters, and activated forms of the amino acid produced in situ using condensing agents, e.g. dicyclohexylcarbodiimide, carbonyldiitmidazole, O-(benzotriazol-yl)-N,N, Nxe2x80x2,Nxe2x80x2-bis(pentamethylene)uronium hexafluorophosphate, O-(benzotriazo-1-yl)-N,N,Nxe2x80x2,Nxe2x80x2-bis(tetra-methylene)uronium hexafluorophosphate, (benzotriazol-1-yloxy)-tripyrrolidinophosphonium hexafluorophosphate, (benzotriazol-1-yloxy)-tris(dimethylamino)phosphonium hexafluorophosphate or O-(benzotriazol-1-yl)-N,N,Nxe2x80x2,Nxe2x80x2-tetramnethyluronium hexafluorophosphate.
The mixed anhydrides corresponding to the amino acid of formula XIII can be prepared by reacting the amino acid of formula XIII with a chloroformic acid ester, for example a chloroformic acid alkyl ester, preferably isobutyl chloroformate, i desired in the presence of an acid-binding agent, such as an inorganic or organic base, for example a tertiary amine, e.g. triethylamine, pyridine, N-methylpiperidine or N-methylmorpholine.
The reaction of the amino acid of formula XIII, or of a carboxy-activated derivative of the amino acid of formula XIII, with an amine of formula XII is carried out in an inert diluent, such as an aromatic, non-aromatic or halogenated hydrocarbon, for example a chlorinated hydrocarbon, e.g. methylene chloride or toluene; a ketone, e.g. acetone; an ester, e.g. ethyl acetate; an amide, e.g. dimethylformamide; a nitrile, e.g. acetonitrile; or an ether, e.g. tetrahydrofuran, dioxane, diethyl ether or tert-butyl methyl ether; or in a mixture of those inert difuents, if desired in the presence of an acid-binding agent, e.g. an inorganic or organic base, for example a tertiary amine, e.g. triethylamine, pyrdine, N-methylpiperidine or N-methylmorpholine, at temperatures of from xe2x88x9280 to +150xc2x0 C., preferably from xe2x88x9240 to +40xc2x0 C.
In a second step, a compound of formula XIV is reacted with a compound of formula V.
The reaction of a compound of formula XIV with a compound of formula V is carried out in an inert diluent. The following may be mentioned as examples: aromatic, non-aromatic or halogenated hydrocarbons, for example toluene or methylene chloride; ketones, for example acetone; esters, for example ethyl acetate; amides, for example dimethylformamide; nitriles, for example acetonitrile; ethers, for example tetrahydrofuran, dioxane, diethyl ether or tert-butyl methyl ether; alcohols, for example methanol, ethanol, n-butanol, isopropanol or tert-butanol; dimethyl sulfoxide; or water; or mixtures of those inert diluents. The reaction of a compound of formula XIV with a compound of formula V is carried out if desired in the presence of an acid-binding agent. Suitable acid-binding agents include inorganic or organic bases, for example alkali metal or alkaline earth metal hydroxides, alcoholates or carbonates, e.g. sodium hydroxide, potassium hydroxide, sodium methanolate, potassium methanolate, sodium ethanolate, potassium ethanolate, sodium tertbutanolate, potassium tert-butanolate, sodium carbonate or potassium carbonate. The temperatures are from xe2x88x9280 to +200xc2x0 C., preferably from 0 to +120xc2x0 C.; or the reaction is carried out as described under Process c).
In a third step, compounds of formula XV are subjected to acid hydrolysis. The reaction of a compound of formula XV with an inorganic or organic acid, for example a mineral acid, e.g. hydrochloric acid or sulfuric acid, or a carboxylic acid, e.g. acetic acid or trifluoroacetic acid, or a sulfonic acid, e.g. methanesulfonic acid or p-toluenesulfonic acid, is carried out if desired in an inert diluent, such as an aromatic, non-aromatic or halogenated hydrocarbon, for example a chlorinated hydrocarbon, e.g. methylene chloride or toluene; a ketone, e.g. acetone; an ester, e.g. ethyl acetate; an ether, e.g. tetrahydrofuran or dioxane; or water, at temperatures of from xe2x88x9240 to +150xc2x0 C. It desired, it is also possible to use mixtures of different acids and of different inert diluents, or the acid itself may serve as the diluent.
The compounds of formula I are oils or solids at room temperature and are distinguished by valuable microbicidal properties. They can be used in the agricultural sector or related fields preventively and curatively in the control of plant-destructive microorganisms. The compounds of formula I according to the invention are distinguished at low rates of concentration not only by outstanding microbicidal, especially fungicidal, activity but also by being especially well tolerated by plants.
Surprisingly, it has now been found that the compounds of formula I have for practical purposes a very advantageous biocidal spectrum in the control of phytopathogenic microorganisms, especially fungi. They possess very advantageous curative and preventive properties and are used in the protection of numerous crop plants. With the compounds of formula I it is possible to inhibit or destroy phytopathogenic microorganisms that occur on various crops of useful plants or on parts of such plants (fruit, blossom, leaves, stems, tubers, roots), while parts of the plants which grow later also remain protected, for example, against phytopathogenic fungi.
The novel compounds of formula I prove to be effective against specific genera of the fungus class Fungi imperfecti (e.g. Cercospora), Basidiomycetes (e.g. Puccinia) and Ascomycetes (e.g. Erysiphe and Venturia) and especially against Oomycetes (e.g. Plasmopara, Peronospora, Pythium and Phytophthora). They therefore represent in plant protection a valuable addition to the compositions for controlling phytopathogenic fungi. The compounds of formula I can also be used as dressings for protecting seed (fruit, tubers, grains) and plant cuttings from fungal infections and against phytopathogenic fungi that occur in the soil.
The invention relates also to compositions comprising compounds of formula I as active ingredient, especially plant-protecting compositions, and to the use thereof in the agricultural sector or related fields.
In addition, the present invention includes the preparation of those compositions, wherein the active ingredient is homogeneously mixed with one or more of the substances or groups of substances described herein. Also included is a method of treating plants which is distinguished by the application of the novel compounds of formula I or of the novel compositions.
Target crops to be protected within the scope of this invention comprise, for example, the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucurbitaceae (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamon, camphor) and plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, and also ornamentals.
The compounds of formula I are normally used in the torm of compositions and can be applied to the area or plant to be treated simultaneously or in succession with other active ingredients. Those other active ingredients may be fertilisers, micronutrient donors or other preparations that influence plant growth. It is also possible to use selective herbicides or insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of those preparations, if desired together with further carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology.
The compounds of formula I can be mixed with other active ingredients, for example fertilisers, micronutrient donors or other crop protection products, especially other fungicides, with the result that unexpected synergistic effects may occur. Preferred mixing partners are: azoles, such as azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole;
pyrimidinyl carbinols, such as ancymidol, fenarimol, nuarimol;
2-amino-pyrimidines, such as bupirimate, dimethirimol, ethirimol;
morpholines, such as dodemorph, fenpropidin, fenpropimorph, spiroxamin, tridemorph;
anilinopyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil;
pyrroles, such as fenpiclonil, fludioxonil;
phenylamides, such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl;
benzimidazoies, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole; dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozolin;
carboxamides, such as carboxin, fenturam, flutolanil, mepronil, oxycarboxin, thifluzamide;
guanidines, such as guazatine, dodine, iminoctadine;
strobilurines, such as azoxystrobin, kresoxim-methyl, metominostrobin, SSF-129, CGA 279202;
dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram;
N-halomethylthio, such as captafol, captan, dichlofluanid, fluoromide, folpet, tolyfluanid; copper compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride,
copper sulfate, cuprous oxide, mancopper, oxine-copper;
nitrophenol derivatives, such as dinocap, nitrothal-isopropyl;
organo-P derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl;
various others, such as acibenzolar-S-methyl, anilazine, blasticidin-S, chinomethionat, chloroneb, chlorothalonil, cymoxanil, dichlone, diclomezine. dicloran, diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminum, hymexazol, kasugamycin, methasulfocarb, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin.
Suitable carriers and surfactants may be solid or liquid and correspond to the substances ordinarily employed in formulation technology, such as e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers. Such carriers and additives are described, for example, in WO 95/30651.
A preferred method of applying a compound of formula I, or an agrochemical composition comprising at least one of those compounds, is application to the foliage (foliar application), the frequency and the rate of application depending upon the risk of infestation by the pathogen in question. The compounds of formula I may also be applied to seed grains (coating) either by impregnating the grains with a liquid formulation of the active ingredient or by coating them with a solid formulation.
The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology, and are for that purpose advantageously formulated in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and by encapsulation in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
Advantageous rates of application are normally from 1 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, especially from 25 g to 750 g a.i./ha. When used as seed dressings, rates of from 0.001 g to 1.0 g of active ingredient per kg of seed are advantageously used.
The formulations, i.e. the compositions, preparations or mixtures comprising the compound(s) (active ingredient(s)) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
Further surfactants customarily used in formulation technology will be known to the person skilled in the art or can be found in the relevant technical literature.
The agrochemical compositions usually comprise 0.01 to 99% by weight, preferably 0.1 to 95% by weight, of a compound of formula 1, 99.99 to 1% by weight, preferably 99.9 to 5% by weight, of a solid or liquid adjuvant, and 0 to 25% by weight, preferably 0.1 to 25% by weight, of a surfactant.
Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
The compositions may also comprise further ingredients, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.